TW202015919A - 積層體 - Google Patents
積層體 Download PDFInfo
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- TW202015919A TW202015919A TW108126123A TW108126123A TW202015919A TW 202015919 A TW202015919 A TW 202015919A TW 108126123 A TW108126123 A TW 108126123A TW 108126123 A TW108126123 A TW 108126123A TW 202015919 A TW202015919 A TW 202015919A
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- TW
- Taiwan
- Prior art keywords
- thermoplastic polyurethane
- layer
- polyamide
- laminate
- laminate according
- Prior art date
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Landscapes
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Abstract
本發明提供一種積層體,其係顯示構造色者,且可不損害構造色之顯色構造而進行深衝加工。
本發明之積層體具有聚醯胺層(1)及具備構造色之顯色構造之熱塑性聚胺酯層(2)。作為上述熱塑性聚胺酯層(2),較佳為於與聚醯胺層(1)相接之面相反側之面具有凹凸構造之熱塑性聚胺酯層、或折射率之差為0.03以上之2種熱塑性聚胺酯交替積層而成之層。
Description
本發明係關於一種顯示構造色之積層體。本案主張2018年7月24日於日本提出申請之特願2018-138165號之優先權,將其內容援引於此。
於容器等領域,自先前以來係藉由裝飾表面而提高商品價值。但是,於使用顏料或染料等色素進行加飾之情形時,存在容易褪色之問題。因此,已知利用基於光之繞射、折射、干涉、散射等之顯色即構造色進行加飾。構造色係基於構造之顯色,可不褪色而長期維持鮮明之顯色。
於專利文獻1中記載有一種附接著劑層之加飾膜,其於顯示構造色之加飾膜之背面設置有接著劑層。而且記載有:藉由將上述附接著劑層之加飾膜貼合於基材,並對貼合於基材之上述附接著劑層之加飾膜實施真空成形,可獲得顯示構造色之三維成形體。但是,有接著劑層容易經年劣化,又,若接著差則會產生空隙,於此處產生孔洞而明顯損害美觀的問題。
先前技術文獻
專利文獻
專利文獻1:日本特開2017-7109號公報
[發明所欲解決之課題]
又,對上述加飾膜及基材之積層體進行深衝加工時,於基材較硬之情形時,雖會利用加熱使基材軟化而追隨模具,但若使用熔點高之基材,則必須在高溫下進行加熱成形,存在由於在高溫下進行加熱成形而構造色之顯色構造受到損害之情形。另一方面,於使用柔軟之基材之情形時,即便加熱成形溫度低亦可充分追隨模具,可不損害構造色之顯色構造而成形,但已知柔軟之基材無塑性,難以保持進行深衝加工所得之成形體之形狀。
因此,本發明之目的在於提供一種積層體,其係顯示構造色者,可不損害構造色之顯色構造而進行深衝加工。
本發明之另一目的在於提供一種積層體,其係顯示構造色者,可不損害構造色之顯色構造而進行深衝加工,且可長期維持美觀。
本發明之另一目的在於提供一種使用上述積層體,製造經實施深衝加工之成形體的方法。
[解決課題之技術手段]
本發明人等為了解決上述課題,經進行潛心研究後,結果發現以下事項。
1.聚醯胺與熱塑性聚胺酯藉由化學鍵牢固地接著,因此可不經由接著劑層而積層聚醯胺層與熱塑性聚胺酯層
2.聚醯胺較硬,具有保持成形體之形狀之功能,另一方面,熱塑性聚胺酯富有柔軟性,良好地追隨深衝加工
3.聚醯胺能夠在熱塑性聚胺酯不分解之溫度下軟化而成形
4.藉由化學鍵使聚醯胺與具備構造色之顯色構造之熱塑性聚胺酯接著所得之積層體可不損害由熱塑性聚胺酯形成之構造色之顯色構造而進行深衝加工,可高精度地製造縱橫比大之成形體,獲得之成形體可保持其顯色構造及形狀
本發明係基於該等見解而完成。
即,本發明提供一種積層體,其具有聚醯胺層(1)及具備構造色之顯色構造之熱塑性聚胺酯層(2)。
本發明又提供一種上述積層體,其中,熱塑性聚胺酯層(2)係於與聚醯胺層(1)相接之面相反側之面具有凹凸構造的熱塑性聚胺酯層。
本發明又提供一種上述積層體,其係於熱塑性聚胺酯層(2)之具有凹凸構造之面積層金屬層(3)而成。
本發明又提供一種上述積層體,其中,熱塑性聚胺酯層(2)係由折射率之差為0.03以上之2種熱塑性聚胺酯層之交替積層體所構成之層。
本發明又提供一種上述積層體,其中,構成聚醯胺層(1)之聚醯胺之熔點與構成熱塑性聚胺酯層(2)之熱塑性聚胺酯之分解開始溫度滿足以下之關係式。
聚醯胺之熔點(℃)+10℃≦熱塑性聚胺酯之分解開始溫度(℃)
本發明又提供一種上述積層體,其中,構成聚醯胺層(1)之聚醯胺之末端胺基量為10 mmol/kg以上。
本發明又提供一種上述積層體,其中,構成聚醯胺層(1)之聚醯胺為聚醯胺彈性體。
本發明又提供一種上述積層體,其中,構成熱塑性聚胺酯層(2)之熱塑性聚胺酯為聚酯胺酯(polyesterurethane)彈性體及/或聚醚胺酯(polyetherurethane)彈性體。
本發明又提供一種上述積層體,其用於縱橫比(深度/開口部之內徑)為0.001以上之深衝加工。
本發明又提供一種成形體之製造方法,其藉由對上述積層體實施真空成形、氣壓成形或者真空氣壓成形,而獲得具備縱橫比(深度/開口部之內徑)為0.001以上之凹部或者凸部之成形體。
[發明之效果]
本發明之積層體具有構造色之顯色構造,且可不損害上述構造而進行深衝加工。又,由於可不經由接著劑層而使聚醯胺層(1)與熱塑性聚胺酯層(2)牢固地接著,故而於實施利用真空成形之深衝加工時,於聚醯胺層(1)與熱塑性聚胺酯層(2)之間不產生空隙,可避免由產生空隙所致之孔洞之產生。進而,雖然接著劑層容易經年劣化,但藉由不設置接著劑層,亦可避免因接著劑層之劣化所致之美觀損失。
進而又,本發明之積層體由於具有適度柔軟之熱塑性聚胺酯層(2),故而可良好地追隨模具,高精度地進行深衝加工,由於具備適度硬度之聚醯胺層(1),故而對該積層體進行深衝加工所得之成形體可穩定地保持其形狀。
因此,本發明之積層體可適合使用於深衝加工。
又,藉由本發明之製造方法所得之成形體穩定地具有經高精度地深衝加工之形狀,並且於紫外線照射等下不褪色而可長期維持良好之美觀。因此,例如可適用作為要求顯示構造色之容器等。
[積層體]
本發明之積層體具有聚醯胺層(1)及熱塑性聚胺酯層(2),上述熱塑性聚胺酯層(2)具備構造色之顯色構造。
本發明之積層體由於具有上述構成,故而適於藉由真空成形等進行使用縱橫比例如為0.001以上之凸模或凹模之深衝加工,可不產生裂痕等而良好地追隨模具,形成模具之轉印精度優異之成形體。因此,本發明之積層體可適用於深衝加工用[即,使用縱橫比例如為0.001以上之凸模或凹模之加工用]。
於本說明書中,用於成形之模具(凸模或凹模)之根據下式算出之縱橫比例如為0.001以上,較佳為0.01以上,尤佳為0.05以上,最佳為0.1以上。再者,上述縱橫比之上限例如為10,較佳為4,尤佳為3,最佳為2。
凸模之縱橫比=凸部之高度/凸部之基底部內徑
凹模之縱橫比=凹部之深度/凹部之開口部內徑
(聚醯胺層(1))
本發明中之聚醯胺層為由聚醯胺所構成之至少1層之層。
聚醯胺層之厚度(於由2層以上構成之情形時為總厚度)例如為30~5000 μm,較佳為50~3000 μm,尤佳為200~2000 μm。
又,聚醯胺層(1)之厚度相對於下述熱塑性聚胺酯層(2)之厚度(於具有熱塑性聚胺酯層(4)之情形時,為熱塑性聚胺酯層(2)與熱塑性聚胺酯層(4)之總厚度)1,例如為3~500,較佳為3~200,尤佳為3~40。
若聚醯胺層(1)之厚度為上述範圍,則可良好地進行深衝加工,且藉由深衝加工所得之成形體之形狀保持效果優異。若聚醯胺層(1)之厚度低於上述範圍,則有難以保持藉由深衝加工所得之成形體之形狀的傾向。另一方面,若聚醯胺層(1)之厚度高於上述範圍,則有難以進行深衝加工,產生裂痕或無法使形狀追隨模具而形狀精度降低之傾向。
構成聚醯胺層之聚醯胺藉由化學鍵而與構成熱塑性聚胺酯層(2)之熱塑性聚胺酯牢固地接著。因此,可不經由接著劑層而使聚醯胺層(1)與熱塑性聚胺酯層(2)牢固地接著固定,於藉由真空成形等進行深衝加工時不會產生剝離。因此,可抑制孔洞之產生,可製造美觀性優異之成形體。
上述聚醯胺適度硬,其硬度(例如,蕭氏D硬度)例如為40~90,較佳為45~85,更佳為50~80,特佳為55~75。利用由具備上述硬度之聚醯胺所構成之聚醯胺層,可對深衝加工所得之成形體賦予強韌性,可穩定地保持成形體之形狀。
而且,關於本發明之積層體,構成聚醯胺層之聚醯胺之熔點(℃)與構成熱塑性聚胺酯層(2)之熱塑性聚胺酯之分解開始溫度(℃)滿足以下之關係式就可不損害構造色、或者不損害具備構造色之顯色構造之熱塑性聚胺酯層(2)的顯色構造而進行深衝加工之方面而言較佳。
聚醯胺之熔點(℃)+10℃≦熱塑性聚胺酯之分解開始溫度(℃)
因此,上述熱塑性聚胺酯之分解開始溫度(℃)與上述聚醯胺之熔點(℃)之差[熱塑性聚胺酯之分解開始溫度(℃)-聚醯胺之熔點(℃)]為10℃以上。就可不損害構造色之顯色構造而進行深衝加工之方面而言,上述溫度之差較佳為20℃以上,尤佳為30℃以上。
作為上述聚醯胺之熔點(℃),較佳為250℃以下,更佳為230℃以下,尤佳為200℃以下,最佳為185℃以下,特佳為175℃以下。聚醯胺之熔點之下限例如為約100℃,較佳為110℃。
再者,聚醯胺之熔點可藉由示差掃描熱量分析裝置(DSC)進行測定。
上述聚醯胺含有結晶性聚醯胺及非晶性聚醯胺。於要求透明性之情形時,較佳為使用非晶性聚醯胺。
上述聚醯胺係至少具有含有醯胺鍵之重複單元之化合物,尤其較佳為至少具有由含有醯胺鍵之重複單元賦予特徵之聚合物鏈,上述聚合物鏈係藉由為單體之二胺成分與二羧酸成分之縮聚、或1分子中具有胺基及羧基之胺基酸之縮聚、或為單體之內醯胺類之開環聚合等進行製造。再者,二胺成分、二羧酸成分、分子中具有胺基及羧基之胺基酸、以及內醯胺類可分別單獨使用1種,或組合2種以上使用。
上述二價烴基含有二價脂肪族烴基、二價脂環式烴基、二價芳香族烴基。
作為二價脂肪族烴基,例如可列舉:亞甲基、甲基亞甲基、二甲基亞甲基、伸乙基、伸丙基、三亞甲基等碳數1~20之直鏈或支鏈狀伸烷基;伸乙烯基、1-甲基伸乙烯基、伸丙烯基、1-伸丁烯基、2-伸丁烯基、1-伸戊烯基、2-伸戊烯基等碳數2~20之直鏈或支鏈狀伸烯基;伸乙炔基、伸丙炔基、3-甲基-1-伸丙炔基、伸丁炔基、1,3-伸丁二炔基、2-伸戊炔基、2-伸戊炔基、2,4-伸戊二炔基、2-伸己炔基、1,3,5-伸己三炔基、3-伸庚炔基、4-伸辛炔基、4-伸壬炔基、5-伸癸炔基、6-伸十一炔基、6-伸十二炔基等碳數2~20之直鏈或支鏈狀伸炔基。
二價脂環式烴基為自脂環之結構式去除2個氫原子所得之基,作為上述脂環,例如可列舉:環丙烷、環戊烷、環己烷、環庚烷、環辛烷環等三~二十員之環烷烴環;環戊烯、環己烯環等三~二十員之環烯烴環;全氫萘、降烷、降莰烯、金剛烷、三環[5.2.1.02,6
]癸烷、四環[4.4.0.12,5
.17,10
]十二烷環等橋接環等。上述脂環可具有取代基(例如碳數1~5之烷基等)。又,上述脂環可2個以上經由單鍵或連結基(例如二價脂肪族烴基)鍵結。
二價芳香族烴基為自芳香環之結構式去除2個氫原子所得之基,作為上述芳香環,例如可列舉苯、萘、蒽、茀環等碳數6~20之芳香環。上述芳香環可具有取代基(例如碳數1~5之烷基、碳數3~6之環烷基等)。又,上述芳香環可2個以上經由單鍵或連結基(例如二價脂肪族烴基或二價脂環式烴基)鍵結。
作為上述式(a)中之L1
為二價脂肪族烴基之化合物(=脂肪族二胺),例如可列舉己二胺、三甲基己二胺等。
作為上述式(a)中之L1
為二價脂環式烴基之化合物(=脂環式二胺),例如可列舉雙(對胺基環己基)甲烷、雙(4-胺基-3-甲基環己基)甲烷等。
作為上述式(a)中之L1
為二價芳香族烴基之化合物(=芳香族二胺),例如可列舉間伸茬基二胺(m-xylylenediamine)等。
作為L2
中之二價烴基,可舉與L1
中之二價烴基相同之例。
作為上述式(c)中之L2
為二價脂肪族烴基之化合物(=脂肪族二羧酸),例如可列舉己二酸、十二烷二酸等。
作為上述式(c)中之L2
為二價脂環式烴基之化合物(=脂環式二羧酸),例如可列舉環己烷-1,4-二羧酸等。
作為上述式(c)中之L2
為二價芳香族烴基之化合物(=芳香族二羧酸),例如可列舉間苯二甲酸、對苯二甲酸等。
作為上述1分子中具有胺基及羧基之胺基酸,例如可列舉:丙胺酸、2-胺基丁酸、纈胺酸、正纈胺酸、白胺酸、正白胺酸、第三白胺酸、異白胺酸、絲胺酸、蘇胺酸、半胱胺酸、甲硫胺酸、2-苯基甘胺酸、苯丙胺酸、酪胺酸、組胺酸、色胺酸、脯胺酸等α-胺基酸;3-胺基丁酸等β-胺基酸。
作為上述內醯胺類,例如可列舉:α-內醯胺、β-內醯胺、γ-內醯胺、δ-內醯胺、є-己內醯胺、十一碳-10-內醯胺、十一碳-11-內醯胺、十二碳-12-內醯胺等具有三~十三員環之內醯胺。
作為上述聚醯胺之由含有醯胺鍵之重複單元賦予特徵(或者含有含醯胺鍵之重複單元)之聚合物鏈,尤其是就具備適度之柔軟性之方面而言,較佳為具有下述式(1)所表示之重複單元之聚合物鏈,
(式中,L表示碳數10~15之二價脂肪族烴基,Ad表示醯胺鍵(-CONH-或-NHCO-))。
作為上述碳數10~15之二價脂肪族烴基,較佳為碳數10~15之伸烷基,尤佳為碳數10~14之伸烷基,最佳為碳數10~13之伸烷基。
上述聚醯胺可為僅以上述由含有醯胺鍵之重複單元賦予特徵之聚合物鏈構成之化合物,又,亦可為上述聚合物鏈及其以外之聚合物鏈聚合而成之化合物。再者,聚合形態可為無規型,亦可為嵌段型。
作為上述聚醯胺,尤其是上述由含有醯胺鍵之重複單元賦予特徵之聚合物鏈及其以外之聚合物鏈聚合(尤佳為嵌段聚合)而成之化合物就兼具適度之硬度及柔軟性,可高精度地進行深衝加工,且藉由深衝加工所得之成形體之形狀保持效果優異之方面而言較佳。
作為上述由含有醯胺鍵之重複單元賦予特徵之聚合物鏈及其以外之聚合物鏈聚合而成之化合物,尤其是由含有醯胺鍵之重複單元賦予特徵之聚合物鏈(H)與比上述聚合物鏈(H)柔軟性優異之聚合物鏈(S)聚合(尤佳為嵌段聚合)而成的聚醯胺彈性體就如下方面而言較佳:藉由使上述聚合物鏈(H)發揮作為硬鏈段之作用,使上述聚合物鏈(S)發揮作為軟鏈段之作用,可與構成熱塑性聚胺酯層(2)之熱塑性聚胺酯更牢固地接著;因與僅由硬鏈段所構成之聚醯胺相比,在更低之溫度下軟化,故即便加熱成形溫度低亦可充分地追隨模具,可不損害構造色之顯色構造而成形;以及具備黏彈性特性、適度之硬度、及柔軟性[硬度(蕭氏D硬度)例如為40~80,較佳為50~75,更佳為55~75],可高精度地進行深衝加工,可穩定地保持深衝加工後所得之成形體之形狀。再者,硬度可藉由調整硬鏈段及軟鏈段之比率進行控制。
聚醯胺彈性體之彎曲模數例如為100~3000 MPa,較佳為150~2500 MPa,尤佳為200~2000 MPa,最佳為200~1500 MPa,特佳為200~1000 MPa。聚醯胺彈性體之彎曲模數可藉由依據ISO178之方法進行測定。
作為上述與聚合物鏈(H)相比柔軟性優異之聚合物鏈(S),例如較佳為選自聚醚、聚酯及聚碳酸酯之聚合物鏈,特佳為聚醚鏈。
為上述聚合物鏈(H)與聚合物鏈(S)之嵌段共聚物的聚醯胺彈性體,可藉由使具有反應性末端基之聚合物鏈(S)與上述聚合物鏈(H)之反應性末端基進行共縮聚而製造。作為上述反應性末端基,例如可列舉胺基或羧基。
作為聚合物鏈(S)之聚醚鏈可藉由使二醇成分(共)聚合而製造。
作為上述二醇成分,例如可列舉:乙二醇、丙二醇、伸丁二醇、2-甲基-1,3-丙二醇、己二醇、3-甲基-1,5-戊二醇、2,2-二乙基-1,3-丙二醇、1,9-壬二醇、2-甲基-1,8-辛二醇等脂肪族二醇;二羥基苯、二羥基甲苯、二羥基聯苯、雙酚A等芳香族二酚等。
又,就獲得耐氧化劣化性優異之聚醯胺層之方面而言,形成聚醯胺層之聚醯胺較佳為其末端胺基量例如為10 mmol/kg以上(較佳為10~300 mmol/kg,尤佳為15~200 mmol/kg,最佳為20~150 mmol/kg)。
形成聚醯胺層之聚醯胺之末端胺基量,例如可藉由調整末端胺基濃度高之聚醯胺與末端胺基濃度低之聚醯胺之摻合比率進行控制。
作為聚醯胺,例如可使用商品名「E58S4」(聚醯胺彈性體,Daicel-Evonik股份有限公司製造)等市售品。
可視需要向聚醯胺加入添加劑。作為上述添加劑,例如可列舉:無機填料、有機填料、玻璃纖維、碳纖維、調光材料、光吸收劑(紫外線、藍光、紅外線等)、著色劑、熱穩定劑、光穩定劑、抗氧化劑、塑化劑、難燃劑、抗靜電劑、黏度調整劑等。上述添加劑之含量相對於聚醯胺100重量份,例如為約0~20重量份。
(熱塑性聚胺酯層(2))
本發明中之熱塑性聚胺酯層(2)為由熱塑性聚胺酯(TPU)所形成之層,具備構造色之顯色構造。
構成熱塑性聚胺酯層(2)之熱塑性聚胺酯適度柔軟,關於其硬度,蕭氏A硬度例如為50~96(較佳為60~96),蕭氏D硬度例如為30~60(較佳為30~50)。因此,於藉由真空成形進行深衝加工時,可良好地追隨模具,高精度地轉印模具之形狀。
熱塑性聚胺酯層(2)之厚度(於下述具有熱塑性聚胺酯層(4)之情形時,為熱塑性聚胺酯層(2)與熱塑性聚胺酯層(4)之總厚度)例如為10~1000 μm,較佳為30~500 μm,尤佳為50~250 μm。
又,熱塑性聚胺酯層(2)之厚度(於下述具有熱塑性聚胺酯層(4)之情形時,為熱塑性聚胺酯層(2)與熱塑性聚胺酯層(4)之總厚度)相對於聚醯胺層(1)之厚度1,例如為0.05~500,較佳為0.1~200,更佳為0.1~40,尤佳為0.1~10,最佳為0.1~1.0。
若熱塑性聚胺酯層(2)之厚度為上述範圍,則於藉由真空成形進行深衝加工時,可良好地追隨模具,高精度地轉印模具之形狀,獲得之成形體可良好地維持其形狀。若熱塑性聚胺酯層(2)之厚度低於上述範圍,則有成形加工性降低之傾向。另一方面,若熱塑性聚胺酯層(2)之厚度高於上述範圍,則有難以維持成形體之形狀之傾向。
構造色之顯色構造係引起光之繞射、折射、干涉或者散射之構造。作為顯色構造之形成方法,例如可列舉以下之方法等。
[1]於熱塑性聚胺酯層(2)之表面設置產生光之波長或者光之繞射與干涉之微細構造(例如3 μm以下之凹部或凸部)之方法
[2]交替積層折射率不同之熱塑性聚胺酯層(2)之方法
因此,作為本發明中之熱塑性聚胺酯層(2),於製成本發明之積層體之情形時,含有於光入射之面相反側之面具有引起光之繞射、折射、干涉或者散射之微細構造之熱塑性聚胺酯層[=熱塑性聚胺酯層(2-1)]、及折射率不同之熱塑性聚胺酯層交替積層而成之層(2-2)[=熱塑性聚胺酯層(2-2)]。
上述[1]中之微細構造較佳設置於與膜之光入射面為相反側之表面,例如可舉直線狀之凹部或凸部以微米尺寸之週期並列之構造。若使光向具備此種構造之熱塑性聚胺酯層自與具有該構造之面為相反側之面入射,則藉由入射光之繞射及干涉而出現干涉條紋(虹色)。
上述微細構造除上述以外,可列舉三角屋頂型、梯形屋頂型、半球屋頂型、半橢圓球屋頂型等三維形狀之微細凹部或凸部於二維方向上無規排列之構造。再者,排列之多個凹部可全部為同一深度,亦可不同深度之凹部混合存在。又,排列之多個凸部可全部為同一高度,亦可不同高度之凸部混合存在。若使光向具備此種構造之熱塑性聚胺酯層自與具有該構造之面為相反側之面入射,則入射光之一部被反射,另一部分透過,對光之光彩、鮮度產生不規則地變化之1/f波動,發揮強調光之明暗之效果。
上述[1]中之微細構造,例如可藉由在熱塑性聚胺酯層之一表面實施蝕刻或壓印成形等而形成。
作為上述[2]中之交替積層折射率不同之熱塑性聚胺酯層之方法,較佳為交替積層折射率不同之2種熱塑性聚胺酯層,尤佳為積層30層以上(進而較佳為200層以上)。
作為上述折射率不同之熱塑性聚胺酯層,較佳為折射率差例如為0.03以上(較佳為0.05以上,尤佳為0.10以上)之2種熱塑性聚胺酯層,尤佳為由折射率之差例如為0.03以上之2種熱塑性聚胺酯層之交替積層體所構成之層。熱塑性聚胺酯層之折射率之調整,例如係藉由向形成上述層之熱塑性聚胺酯添加填料(例如二氧化矽填料)等而進行。
於上述[2]中之交替積層折射率不同之熱塑性聚胺酯層之方法中,藉由將熱塑性聚胺酯層之400~1000 nm之波長區域之相對反射率設為30%以上(較佳為40%以上,尤佳為80%以上),可獲得金屬色調之構造色。
(熱塑性聚胺酯)
形成熱塑性聚胺酯層(2)之熱塑性聚胺酯係具有胺酯鍵(-NHCOO-)之聚合物,係藉由多異氰酸酯、高分子量多元醇及鏈伸長劑之加成反應所得之橡膠彈性體。熱塑性聚胺酯具備藉由多異氰酸酯與鏈伸長劑之反應所形成之硬鏈段以及藉由多異氰酸酯與高分子量多元醇之反應所形成之軟鏈段。
熱塑性聚胺酯之分解開始溫度為約230~250℃,若為該溫度以上,則由於熱塑性聚胺酯分解,產生CO2
或H2
O氣體,故而損害構造色之顯色構造。
熱塑性聚胺酯總量中之上述硬鏈段所占之比率,就成形加工性優異之方面而言,例如為30~60重量%。若硬鏈段所占之比率低於上述範圍,則柔軟性變得過高,於實施真空成形時有損害構造色之顯色構造之虞。另一方面,若硬鏈段所占之比率高於上述範圍,則柔軟性降低,有難以高精度地進行深衝加工之傾向。
熱塑性聚胺酯例如可藉由如下方法(預聚物法)進行製造:使多異氰酸酯與高分子量多元醇反應,獲得於分子末端具有異氰酸基之異氰酸基末端預聚物,使獲得之異氰酸基末端預聚物與鏈伸長劑反應。
作為多異氰酸酯、高分子量多元醇及鏈伸長劑之使用量,多異氰酸酯中之異氰酸基相對於高分子量多元醇及鏈伸長劑中之羥基之總量的當量比(NCO/OH)例如為0.8~1.2(較佳為0.9~1.1,尤佳為0.98~1.05)之範圍。
作為上述具有異氰酸基之化合物,較佳為多異氰酸酯化合物,例如可列舉:2,4-甲伸苯基二異氰酸酯、2,6-甲伸苯基二異氰酸酯、1,3-二甲苯二異氰酸酯、1,4-二甲苯二異氰酸酯、伸茬基二異氰酸酯、1,5-萘二異氰酸酯、間-伸苯基二異氰酸酯、對-伸苯基二異氰酸酯、二苯基甲烷二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、4,4'-二苄基二異氰酸酯、異佛爾酮二異氰酸酯、六亞甲基二異氰酸酯、二環己基甲烷二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、三苯甲烷三異氰酸酯、二亞甲基三苯基三異氰酸酯、以及上述二異氰酸酯化合物中具備芳香環之化合物之氫化物(例如氫化伸茬基二異氰酸酯、氫化二苯基甲烷二異氰酸酯等)等。
作為上述高分子量多元醇,較佳為具有2個以上之羥基,且數量平均分子量為400以上(例如400~5000,較佳為1000~4000,更佳為1500~3000)之化合物。作為上述化合物,例如可列舉:聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、丙烯醯基(acryl)多元醇、環氧多元醇、天然油多元醇、聚矽氧多元醇、氟多元醇、聚烯烴多元醇、聚胺酯多元醇等。
作為上述高分子量多元醇,尤其是聚醚多元醇及/或聚酯多元醇就柔軟性之方面而言較佳。因此,作為本發明中之熱塑性聚胺酯,較佳為使多異氰酸酯與聚醚多元醇及/或聚酯多元醇反應所得之化合物(即聚酯胺酯彈性體及/或聚醚胺酯彈性體)。
作為上述聚醚多元醇,例如可列舉:聚乙二醇、聚丙二醇、聚丁二醇、聚乙烯聚丙烯二醇、聚乙烯聚丁烯二醇、聚丙烯聚丁烯二醇等聚氧C2 - 4
伸烷基二醇。
作為上述聚酯多元醇,例如可列舉聚己內酯多元醇、聚戊內酯多元醇等內酯系多元醇等。
作為上述鏈伸長劑,例如可列舉:包含乙二醇、丙二醇、丁二醇、1,4-丁二醇、丁烯二醇、丁炔二醇、茬二醇、戊二醇、1,4-伸苯基-雙-β-羥基乙基醚、1,3-伸苯基-雙-β-羥基乙基醚、雙(羥基-甲基-環己烷)、己二醇、以及硫代雙乙醇之二醇;乙二胺、丙二胺、丁二胺、己二胺、環己二胺、苯二胺、甲伸苯基二胺、伸茬基二胺、3,3'-二氯聯苯胺、3,3'-二硝基聯苯胺等二胺;乙醇胺、胺基丙醇、2,2-二甲基丙醇胺、3-胺基環己醇、對胺基苄醇等烷醇胺。
作為熱塑性聚胺酯,例如可使用商品名「Higress」(Sheedom股份有限公司製造)等市售品。
可視需要向熱塑性聚胺酯加入添加劑。作為上述添加劑,例如可列舉:調光材料、光吸收劑(紫外線、藍光、紅外線等)、著色劑、熱穩定劑、光穩定劑、抗氧化劑、塑化劑、難燃劑、抗靜電劑、黏度調整劑等。上述添加劑之含量相對於熱塑性聚胺酯100重量份,例如為約0~20重量份。
本發明之積層體除聚醯胺層(1)與熱塑性聚胺酯層(2)以外亦可積層其他層,例如於熱塑性聚胺酯層(2)為熱塑性聚胺酯層(2-1)且期望金屬色調之構造色之情形時,較佳為於熱塑性聚胺酯層(2-1)之具有微細構造之面上設置金屬層(3)(例如含有選自鋁、銀、銅、鉻、錫、鎳、氧化矽、硫化鋅等中之至少1種金屬之金屬層(較佳為金屬薄層))。作為設置金屬層之方法,例如可列舉利用蒸鍍之方法或藉由接著劑貼合金屬箔之方法。又,於設置金屬層之情形時,金屬層可設置於熱塑性聚胺酯層(2-1)之具有微細構造之面整體,亦可設置於其一部分。
金屬層(3)之厚度就發揮良好之金屬色調之構造色的方面而言,例如為0.001~10 μm,較佳為0.01~7 μm,尤佳為0.02~5 μm。
於進而設置金屬層(3)之情形時,出於保護金屬層(3)之目的,較佳為進而於其表面(=與熱塑性聚胺酯層(2)相接之面相反側之面)積層熱塑性聚胺酯層(4)。即,本發明之積層體於具有金屬層(3)之情形時,較佳具有聚醯胺層(1)/熱塑性聚胺酯層(2)/金屬層(3)/熱塑性聚胺酯層(4)之構成。
金屬層(3)與熱塑性聚胺酯層(4)可經由接著劑層積層。作為構成上述接著劑層之接著劑,例如可使用丙烯酸系、胺酯系(例如胺酯酯系、胺酯醚系)、環氧系、乙酸乙烯酯系等之慣用之接著劑。其中,就接著強度優異,且不損害真空成形等之成形性之方面而言,較佳為使用胺酯系(例如胺酯酯系、胺酯醚系)接著劑。例如,市售有由東洋莫頓股份有限公司製造之酯系聚胺酯「TM-595」等主劑與硬化劑(商品名「CAT-10L」、「CAT-RT85」等)之組合所構成之乾式層壓接著劑。
接著劑較佳為以硬化後之厚度例如成為0.1~40 μm(較佳為1~30 μm,尤佳為5~20 μm)之範圍進行塗佈。
接著劑之塗佈例如可藉由印刷法、塗佈法等進行。具體而言,可列舉:網版印刷法、遮罩印刷法、套版印刷法、噴墨印刷法、軟版印刷法、凹版印刷法、衝壓、滴塗、擠壓印刷法、絲網印刷法、噴霧、毛刷塗裝等。
本發明之積層體之總厚度可視用途適當進行變更,例如較佳為約0.05~6 mm,尤佳為0.1~2 mm。
本發明之積層體顯示構造色。又,可不損害構造色之顯色構造而實施真空成形等,可製造顯示構造色且良好地轉印模具之形狀(即便為具備高縱橫比之凹部或者凸部之形狀)而成之成形體。因此,本發明之積層體可適合使用於藉由真空成形、氣壓成形或者真空氣壓成形製造顯示構造色之成形體之用途。本發明之積層體尤其可適合使用於藉由真空成形、氣壓成形或者真空氣壓成形製造顯示構造色且具備高縱橫比之凹部或者凸部之成形體之用途。
又,本發明之積層體由於聚醯胺層(1)與熱塑性聚胺酯層(2)不經由接著劑層而藉由化學鍵牢固地接著,故而於實施深衝加工時不會產生剝離。因此,可抑制孔洞之產生,可製造美觀性優異之成形體。又,接著劑容易因經年劣化而變色,又,容易脆化。因此,具備接著劑層之積層體或由上述積層體形成之成形體存在因經年劣化而損害強度或美觀之問題,但若使用本發明之積層體,則可消除由接著劑之經年劣化所致之上述問題。
[成形體之製造方法]
本發明之成形體之製造方法之特徵在於藉由對上述積層體實施真空成形、氣壓成形或者真空氣壓成形而獲得具備縱橫比(深度/開口部之內徑)為0.001以上之凹部或者凸部之成形體。
再者,真空成形係指如下方法:藉由對本發明之積層體進行加熱使之軟化,用上述積層體被覆期望形狀之模具(例如凸模、凹模等),對模具進行真空吸引,而使上述積層體與模具密接而成形。
氣壓成形,係指藉由壓縮空氣代替真空吸引使上述積層體與模具密接,除此以外與真空成形相同的方法。
真空氣壓成形,係指藉由同時或者有時間差地實施真空吸引與壓縮空氣密接而使上述積層體與模具密接,除此以外與真空成形相同的方法。
對積層體進行加熱使之軟化時之加熱溫度(或者成形溫度)較佳為構成熱塑性聚胺酯層(2)之熱塑性聚胺酯之軟化點以上之溫度,且為使構成聚醯胺層(1)之聚醯胺軟化至能夠變形之程度之溫度以上之溫度(例如低於聚醯胺之熔點約5~10℃之溫度),尤其就可不損害熱塑性聚胺酯層(2)之構造色之顯色構造而成形,且可良好地轉印模具之形狀而成形之方面而言,較佳為熱塑性聚胺酯之分解開始溫度以下之溫度(例如較熱塑性聚胺酯之分解開始溫度低5℃以上之溫度,較佳為低10℃以上之溫度,尤佳為低30℃以上之溫度,最佳為低50℃以上之溫度)。因此,作為上述加熱溫度(或者成形溫度),較佳為例如為130~250℃,較佳為150~230℃,尤佳為150~200℃。
若根據本發明之製造方法,可獲得顯示構造色且良好地轉印模具之形狀(即便為具備高縱橫比之凹部或者凸部之形狀)之成形體。
實施例
以下,藉由實施例更具體地對本發明進行說明,但本發明並不限定於該等實施例。
實施例1
(積層體之製造)
將聚醯胺膜(1)[使用結晶性聚醯胺彈性體(末端胺基量:10 mmol/kg以上,熔點:168℃,厚度:0.8 mm,蕭氏D硬度:58,彎曲模數:200 MPa,商品名「E58S4」(Daicel-Evonik股份有限公司製造))形成之膜]以及對單面實施了壓紋加工之熱塑性聚胺酯層/鋁蒸鍍層/熱塑性聚胺酯層(50 μm/0.001~10 μm/100 μm)之積層體(熱塑性聚胺酯之分解開始溫度:230℃,商品名「Urethane Hologram」,村田金箔股份有限公司製造)一面於160℃,進行加熱,一面進行按壓使之貼合,獲得積層體(1)(PA/具有構造色之顯色構造之TPU/鋁蒸鍍層/TPU,總厚度:約950~960 μm)。
(成形體之製造)
對獲得之積層體(1)實施使用具備矩形凹部(深度3 cm,開口部內徑5 cm,縱橫比0.6)之金屬模具之真空成形(加熱溫度:190℃,加熱時間:20秒),獲得成形體(1)。成形體(1)顯示構造色,且形狀精度良好。又,具有適度之硬度,可維持成形體之形狀。
實施例2
(積層體之製造)
使用向末端胺基濃度低之聚醯胺樹脂(結晶性聚醯胺彈性體,末端胺基量:10 mmol/kg以下)摻合末端胺基濃度較高之聚醯胺樹脂(聚醯胺彈性體,末端胺基量:10 mmol/kg以上)所得之聚醯胺組成物,獲得聚醯胺膜(2)(結晶性聚醯胺彈性體,末端胺基量:10 mmol/kg以上,熔點:160℃,厚度:0.8 mm,蕭氏D硬度:70,彎曲模數:1500 MPa)。
使用聚醯胺膜(2)代替聚醯胺膜(1),除此以外與實施例1同樣地獲得積層體(2)(PA/具有構造色之顯色構造之TPU/鋁蒸鍍層/TPU,總厚度:約950~960 μm)。
(成形體之製造)
使用積層體(2)代替積層體(1),除此以外與實施例1同樣地獲得成形體(2)。成形體(2)顯示構造色,且形狀精度良好。又,具有適度之硬度,可維持成形體之形狀。
實施例3
(積層體之製造)
使用向聚醯胺彈性體(非晶性,末端胺基量:10 mmol/kg以上)摻合聚醯胺彈性體(結晶性,末端胺基量:10 mmol/kg以上)所得之聚醯胺組成物,獲得聚醯胺膜(3)(末端胺基量:10 mmol/kg以上,熔點:150℃,厚度:0.8 mm,蕭氏D硬度:65,彎曲模數:380 MPa)。
使用聚醯胺膜(3)代替聚醯胺膜(1),除此以外與實施例1同樣地獲得積層體(3)(PA/具有構造色之顯色構造之TPU/鋁蒸鍍層/TPU,總厚度:約950~960 μm)。
(成形體之製造)
使用積層體(3)代替積層體(1),除此以外與實施例1同樣地獲得成形體(3)。成形體(3)具有高於成形體(1)、(2)之透明度。又,成形體(3)顯示構造色,且形狀精度良好。進而,具有適度之硬度,可維持成形體之形狀。
比較例1
除不使用聚醯胺以外,與實施例1同樣地獲得積層體(4)(具有構造色之顯色構造之TPU/鋁蒸鍍層/TPU=50 μm/0.001~10 μm/100 μm,總厚度:約150~160 μm)。
又,使用積層體(4)代替積層體(1),除此以外與實施例1同樣地獲得成形體(4)。成形體(4)顯示構造色,但過於柔軟而無塑性,無法維持成形體之形狀。
比較例2
使用雙軸延伸PET膜(熔點:260℃,蕭氏D硬度:85,彎曲模數:2500 MPa)代替聚醯胺,除此以外與實施例1同樣地獲得積層體(5)(PET/具有構造色之顯色構造之TPU/鋁蒸鍍層/TPU=300 μm/50 μm/0.001~10 μm/100 μm,總厚度:約450~460 μm)。
又,使用積層體(5)代替積層體(1),除此以外與實施例1同樣地獲得成形體(5)。成形體(5)顯示構造色。但是,積層體(5)過硬,因此對模具之追隨性不佳,獲得之成形體(5)之轉印精度不良。
比較例3
使用真空成形用PET膜(非晶性,熔點:254℃,蕭氏D硬度:65,彎曲模數:2100 MPa,商品名「A-PETFR」,帝人股份有限公司製造)代替聚醯胺,除此以外與實施例1同樣地獲得積層體(6)(PET/具有構造色之顯色構造之TPU/鋁蒸鍍層/TPU=300 μm/50 μm/0.001~10 μm/100 μm,總厚度:約450~460 μm)。
又,使用積層體(6)代替積層體(1),除此以外與實施例1同樣地獲得成形體(6)。成形體(6)顯示構造色。但是,積層體(6)中,PET與具有構造色之顯色構造之TPU的接著不佳,於真空成形時產生隆起而夾帶空氣(產生孔洞),獲得之形成體(6)之外觀不良。
作為以上之彙總,將本發明之構成及其變化附記於以下。
[1]一種積層體,其具有聚醯胺層(1)及具備構造色之顯色構造之熱塑性聚胺酯層(2)。
[2]如[1]記載之積層體,其中,熱塑性聚胺酯層(2)為於與聚醯胺層(1)相接之面相反側之面具有凹凸構造的熱塑性聚胺酯層。
[3]如[2]記載之積層體,其係於熱塑性聚胺酯層(2)之具有凹凸構造之面積層金屬層(3)而成。
[4]如[1]記載之積層體,其中,熱塑性聚胺酯層(2)為由折射率之差為0.03以上之2種熱塑性聚胺酯層之交替積層體所構成之層。
[5]如[1]至[4]中任一項所記載之積層體,其中,構成聚醯胺層(1)之聚醯胺之熔點與構成熱塑性聚胺酯層(2)之熱塑性聚胺酯之分解開始溫度滿足以下之關係式。
聚醯胺之熔點(℃)+10℃≦熱塑性聚胺酯之分解開始溫度(℃)
[6]如[1]至[5]中任一項所記載之積層體,其中,構成聚醯胺層(1)之聚醯胺之末端胺基量為10 mmol/kg以上。
[7]如[1]至[6]中任一項所記載之積層體,其中,構成聚醯胺層(1)之聚醯胺含有具有式(1)所表示之重複單元之聚合物鏈。
[8]如[1]至[7]中任一項所記載之積層體,其中,構成聚醯胺層(1)之聚醯胺為聚醯胺彈性體。
[9]如[1]至[8]中任一項所記載之積層體,其中,構成聚醯胺層(1)之聚醯胺之彎曲模數為100~3000 MPa。
[10]如[1]至[9]中任一項所記載之積層體,其中,構成聚醯胺層(1)之聚醯胺之蕭氏D硬度為40~80。
[11]如[1]至[10]中任一項所記載之積層體,其中,構成熱塑性聚胺酯層(2)之熱塑性聚胺酯為聚酯胺酯彈性體及/或聚醚胺酯彈性體。
[12]如[1]至[11]中任一項所記載之積層體,其中,構成熱塑性聚胺酯層(2)之熱塑性聚胺酯之蕭氏D硬度為30~60。
[13]如[1]至[12]中任一項所記載之積層體,其中,相對於聚醯胺層(1)之厚度1,熱塑性聚胺酯層(2)之厚度為0.05~40。
[14]如[1]至[13]中任一項所記載之積層體,其中,相對於熱塑性聚胺酯層(2)之厚度1,聚醯胺層(1)之厚度為3~40。
[15]如[1]至[14]中任一項所記載之積層體,其用於縱橫比(深度/開口部之內徑)為0.001以上之深衝加工。
[16]一種[1]至[15]中任一項所記載之積層體之用途,其用於根據下式算出之縱橫比為0.001以上之深衝加工。
縱橫比=衝型之深度/衝型之開口部之內徑
[17]一種[1]至[15]中任一項所記載之積層體之用途,其用於使用根據下式算出之縱橫比為0.001以上之凸模或凹模之深衝加工。
凸模之縱橫比=凸部之高度/凸部之基底部內徑
凹模之縱橫比=凹部之深度/凹部之開口部內徑
[18]一種成形體之製造方法,其使用[1]至[15]中任一項所記載之積層體,獲得具備縱橫比(深度/開口部之內徑)為0.001以上之凹部或者凸部之成形體。
[19]一種成形體之製造方法,其藉由對[1]至[15]中任一項所記載之積層體實施真空成形、氣壓成形或者真空氣壓成形,而獲得具備縱橫比(深度/開口部之內徑)為0.001以上之凹部或者凸部之成形體。
[產業上之可利用性]
若根據本發明之積層體,可不損害構造色而進行深衝加工。因此,本發明之積層體例如可適用作為要求顯示構造色之容器等之原料。
無。
無
Claims (11)
- 一種積層體,其具有聚醯胺層(1)及具備構造色之顯色構造之熱塑性聚胺酯層(2)。
- 如請求項1所述之積層體,其中,熱塑性聚胺酯層(2)係於與聚醯胺層(1)相接之面相反側之面具有凹凸構造的熱塑性聚胺酯層。
- 如請求項2所述之積層體,其係於熱塑性聚胺酯層(2)之具有凹凸構造之面積層金屬層(3)而成。
- 如請求項1所述之積層體,其中,熱塑性聚胺酯層(2)係由折射率之差為0.03以上之2種熱塑性聚胺酯層之交替積層體所構成之層。
- 如請求項1至4中任一項所述之積層體,其中,構成聚醯胺層(1)之聚醯胺之熔點與構成熱塑性聚胺酯層(2)之熱塑性聚胺酯之分解開始溫度滿足以下之關係式: 聚醯胺之熔點(℃)+10℃≦熱塑性聚胺酯之分解開始溫度(℃)。
- 如請求項1至5中任一項所述之積層體,其中,構成聚醯胺層(1)之聚醯胺之末端胺基量為10 mmol/kg以上。
- 如請求項1至7中任一項所述之積層體,其中,構成聚醯胺層(1)之聚醯胺為聚醯胺彈性體。
- 如請求項1至8中任一項所述之積層體,其中,構成熱塑性聚胺酯層(2)之熱塑性聚胺酯為聚酯胺酯(polyesterurethane)彈性體及/或聚醚胺酯(polyetherurethane)彈性體。
- 如請求項1至9中任一項所述之積層體,其用於縱橫比(深度/開口部之內徑)為0.001以上之深衝加工。
- 一種成形體之製造方法,其藉由對請求項1至10中任一項所述之積層體實施真空成形、氣壓成形或者真空氣壓成形,而獲得具備縱橫比(深度/開口部之內徑)為0.001以上之凹部或者凸部之成形體。
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- 2019-07-24 TW TW108126123A patent/TWI805810B/zh active
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US20210370649A1 (en) | 2021-12-02 |
DE112019003758T5 (de) | 2021-04-08 |
JP7263357B2 (ja) | 2023-04-24 |
TWI805810B (zh) | 2023-06-21 |
JPWO2020022204A1 (ja) | 2021-08-19 |
US11766850B2 (en) | 2023-09-26 |
WO2020022204A1 (ja) | 2020-01-30 |
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